Ocean acidification - part 2

Are oceans becoming more acidic and is this a threat to
marine life? How does it work?

By Dr J Floor Anthoni (2007-2010, updated from time to time)
www.seafriends.org.nz/issues/global/acid2.htm

Ocean acidification has become a major scare
in the scientific literature and the media. This chapter shows what is
known about carbon dioxide in the oceans in order to understand how ocean
acidification works and what effects it could cause. Also new insight is
cast on CO2 processes in a living Earth.

What is the carbon
situation?Over
the past two decades scientists gained a fair understanding of where all
carbon is found and how much of it circulates between atmosphere, land
and sea, although significant differences can be found among authors. As
one can see, the human contribution is about 8Pg carbon per year (8Gt,
billions of tons) against a global respiration rate of about 100-250Pg/y
(fossil fuel alone: 2%, some say 3%). It is thought that this contribution
is the cause of the observed increase in the concentration of CO2 in the
atmosphere from a supposed 180ppm pre-industrial to a present-day 400ppm.
So there is good certainty that the amount of CO2 in the air is rising.
The critical question remains why? Many scientists believe it is caused
by the burning of fossil fuels and other human activities, but considering
the presence of a huge reservoir of carbondioxide in the ocean, one should
ask whether the tail is wagging the dog (see box below).
[for more about where the carbon is locked up on land, look at
soil54.gif
]

This
diagram shows the latest figures (after Holmen, 2000) with residence times
and today's atmospheric carbon at 700Gt. The land has been split
in two compartments and the oceans in three. Apparently plants assimilate
122Gt/y in photosynthesis, with leaves dying after 5 years, and their stems
and decaying wood estimated at 1100Gt, decaying in 20 years while returning
60Gt back to the air. Of the total, only 2Gt is sequestered. From this
less than 0.1Gt is sequestered for 1000y in fossil fuels and shales.
The oceans have been split into three compartments, with mainly the
surface ocean interacting with the atmosphere, photosynthesising and respiring/decaying
100GtC/y while sequestering 2 GtC/y. Only 0.3 GtC/y rains down in the form
of carbonate oozes of marine sediments of which a massive 30 million GtC
exists, to be circulated to the surface through ocean floor spreading,
subduction and volcanic activity, which takes 100 million years.

I have some reservations about this diagram:

of the plants, their soils have been neglected, including the fast turnover
of CO2 between them. Batjes (1996) estimates soil carbon at 2200GtC ("the
soil is the largest terrestrial pool of organic carbon"), a substantial
addition to above diagram.

a cycle of 122 Gt on a living biomass of 70Gt living plant matter cannot
result in residency time of 5y

fossil oil and shales come from the sea, not the land but peat and coal
do.

the figures differ too much from previously published ones.

values for sequestration are guessed at, being the small difference between
two large figures.

residence time of CO2 in atmosphere is highly contentious, estimated between
2 and 20 years

residence times for deep ocean water have been measured to be less than
thousand years, not 100,000.

carbon exchange with sea soil is not shown.

river deposits into the sea are not shown

forest burning and habitat change are not shown.

deep carbon clathrate deposits are not taken account of.

Compare this diagram of global carbon dioxide fluxes
and reservoirs with the previous one and notice the large differences.

What all this means is that we know very little for sure about the most
important process on Earth.

Does
the tail wag the dog?Present-day thinking goes
as follows: human-made CO2 is extra to the normal carbon cycle. It therefore
accumulates in the atmosphere, which also makes the sea more acidic. Thus human CO2 => atmosphere
=> ocean => oceans more acidic => oceans store C

But the ocean is vast and
CO2 has an uncanny affinity with water. Thus oceans stabilise the CO2 fluctuations
from the seasons and the differences between ocean and land. The oceans
contain far more CO2 than air: 38,000Gt versus 700 Gt (about 50 times).
A slight warming of the ocean expels CO2 while becoming more acidic, about
1000-1500Gt per degree C (see graph in part
1) .

Thus ocean warming =>
releases CO2 to water => releases CO2 to air => higher CO2 levels in air.Only very little warming
is required to match today's increase in CO2 in air.

Which scenarios are most
likely? Indeed Faure estimated from his studies of past land cover that
during the transition from the last ice age to the present inter-glacial,
some 4000Gt CO2 (1200GtC) was transferred from the ocean to the continental
biosphere (through the carbon pipe, see further).
Compare this with 700GtC in the atmosphere and 1170GtC in the biosphere
as mentioned above. Note that Faure's estimate of terrestrial biomass today
is 2300GtC.

The
relationship between ocean temperature and CO2 in the atmosphere is shown
here, as graphed by Prof Lance Endersbee (www.atse.org.au), showing a near-linear
relationship with little deviation from it (R2=0.996, a measure
of match). As temperature rises, so does the concentration of CO2 in the
atmosphere. Note that this graph does not prove who drives whom, but as
atmospheric temperature stabilised and even declined in the years 1998-2008,
while oceans continued to warm, it becomes defensible that rising ocean
temperature is the driving force behind rising concentrations of CO2, as
explained above. However, critics argue that the 21-year averaging of temperature
will always give a straight line of sorts, but to simulate deep warming
from surface variations, by long-term averaging is entirely proper.Note that a rise of 0.1
ºC corresponds to an increase of about 15ppmv in the atmosphere (150ppmv
per ºC ~ 300Gt/ ºC carbon. [compare with our estimate above]
). Cumulative anthropogenic emission over the industrial age is estimated
at about 140ppmv over two centuries, which is about the same as an ocean
warming of 1 ºC.Note that Endersbee's figure is a blessing in disguise,
because it is impossible to calculate or estimate CO2 outgassing from the
solubility
in water. For instance:

the effect of salt and other
minerals on solubility is not known

the effective depth of the warming
sea contributing to outgassing is not known

the effect needs to be integrated
over the entire globe, taking account of local sea temperatures

the effect of the carbon
pump through the deep sea is unknown as cold seas absorb CO2 while
warm seas expel it.

For instance, assuming a rate
of 3%/ºC degassing at global average temperature (see part1),
and an amount of 38,000Gt (C) dissolved CO2, the amount outgassed for the
whole ocean would be 1,140Gt/ºC (Carbon) or 635ppmv/ºC for the
whole ocean. The surface 100m with 600Gt C is perturbed a few times per
year, contributing almost instantly to warming, or 18 Gt/ºC (carbon),
or 10ppmv/ºC. Remember 10ppm/ºC for each 100m of ocean depth.
Endersbee's figure of ~300 lies comfortably between 18 and 1140.Reader, as you may notice,
there is a lot of uncertainty here. The 'Keeling curve' from Mauna Loa
may eventually dip again. One thing is certain: as long as the oceans
warm up, it outgasses CO2. Thus the oceans, while warming, do not absorb
the extra CO2 from fossil fuel, but they do recycle it. One cannot have
it both ways.

Update Aug 2011: Endersbee's
curve is heavily contested mainly because he took a period in which both
temperature and CO2 were rising. However when earlier data is included
to 1960, the linearity distorts. More important, the new measurements of
missing oxygen climate4#missing_oxygen
lead to the conclusion that seas have been absorbing CO2 for several decades,
rather than exhaling it.

Present IPCC thinking
and what could be possibleThe oceans also play a role
in the IPCC's logic about Anthropogenic Global Warming (AGW):

1) humans burn fossil
fuel => more CO2 in air => global warming

but there is a missing sink,
because the cumulatively added CO2 has mainly disappeared from air:

2) more CO2 in air =>
some absorbed by plants + some absorbed by oceans + what remains in air

However, there is almost
100% uncertainty about how much the oceans absorb. So it is equally possible
that the oceans are the important driver of CO2:

3) expelled CO2 from oceans
+ fossil fuel burning => more plant growth + some in air for faster growth

Thus temperature follows
its own course, stabilised by the ocean and independent of CO2.

Where are the carbon sinks?As the block diagram above suggests, both the sea and the land sequester
2 of the 6-8 GtC/y anthropogenic (human made) CO2 or about 50%, but where
does it go? At the bottom of the diagram, a total of 0.4 GtC/y is sequestered
'permanently' in sediments. Can the terrestrial biosphere keep storing
2% additional carbon per year? Eventually trees die and their wood is decomposed
back into CO2, otherwise the amount of standing vegetation would double
in 60 years (not altogether impossible). In this respect the sea is in
a better position, as it already contains some 40,000 Gt, as in 60 years
time it would have increased by only 0.3% GtC. Thus the sea will most likely
be the ultimate carbon sink, and for this reason
also the ultimate source of carbon when the temperature increases.

"Eighty percent of inputs from land to sea are deposited here [in
coastal margins], and 85% of organic carbon and 45% of inorganic carbon
are buried in the ocean margin sediments (Gattuso et al., 1998a; Wollast,
1998; Chen et al., 2003)". This suggests that carbon from the terrestrial
biosphere finds its way to the sea, carried by rain water and rivers,
not shown in the diagram.

"Ocean margins are also heavily impacted by human activities, as
nearly 40% of the global population lives within 100 km of the coastline
(Cohen et al., 1997). Since the onset of the Industrial Revolution, burning
of fossil fuels and land-use changes have caused substantial increases
in both atmospheric CO2 concentration and in the delivery of organic matter
and nutrients to ocean margins (Mackenzie, 2003). Such changes could alter
the role of this system and considerably affect important processes such
as air-sea CO2 exchange".

As
the sea warms, the warmer water remains on top because it is lighter, which
results in a layer of warm water above a thermocline, below which
the colder water is found. Thus the water above the thermocline,
also called the mixed layer, is more in contact with the atmosphere
than the water below it, which cannot reach the surface. This map shows
the depth of the mixed layer, with the warm tropics being very shallow
and the cold subantarctic very deep. Notice the rather strange false colour
scale below it. It so happens that warm water breathes CO2 out whereas
cold water breathes it in. Notice also that the mixed layer depth
changes with the seasons. The next question is: how does temperature affect
the in- and ex-haling of CO2?

Much
effort has been spent travelling the world's ocean to measure the net flux
(flow) of CO2 in and out of the ocean, and the map here shows its result.
Where the water warms and wells up from the deep, the release of CO2 is
dominant. Conversely where the water cools and sinks, CO2 dissolves into
the water. The figures are in trillions of grams or billions of kg or millions
of tons carbon (MtC) per 4x5 degree area. Note that these 'squares' become
significantly smaller towards the poles, and also that the pattern changes
with the seasons. Most importantly, from the complex dataset it cannot
be determined whether the oceans are over-all breathing in or breathing
out, let alone by how much. A quick impression is that there is more blue
and purple (CO2 in) than yellow and red (CO2 out).

Note that scientists cannot actually measure the flow of CO2. They measure
the partial pressure of CO2 (pCO2aq) in the water and above it where pCO2
is equal to ppmv CO2, and then computers do the rest. Whether this is true
to nature, is not known, also because wind plays a role.

Reader did you notice the high level of uncertainty here?

Reservoir or pipe?Atmospheric scientists treat the atmosphere as a reservoir, with inputs
and outputs, much the way bean-counters treat a company balance sheet.
But is it a correct model? Nearly all of the CO2 added by deforestation
and the burning of fossil fuels has mysteriously disappeared, absorbed
by plants and plankton. As both humans and the sea add more CO2 to the
air, it keeps disappearing at an ever faster rate. But plants cannot sequester
CO2 at a faster rate if its concentration in air remains the same.

Note that all plants and plankton are competing for the one and
only resource of CO2 in air, and species who do it better than others,
come out winning. However, faster absorption can happen only if also the
concentration in air increases. In other words, the atmosphere acts more
like a pipe than a reservoir. This pipe can transport more
gas only if its pressure (concentration) increases.
The pipe concept may explain why a transport of 1,000-1,500Gt
(carbon) from sea to land can be achieved with an increased CO2 concentration
of only 150Gt (carbon) in a pipe of 700Gt. But how does this
work?

The
graph shows how ecologists see the growth of populations. The green curve
shows growth in biomass over time, from a near-zero beginning in a world
without limitations. The rate of growth here depends only on how much offspring
survives, and follows an exponential (explosive) curve. However, gradually
some important resource becomes inadequate to sustain this growth, and
the population grows ever more slowly until it reaches a maximum for which
the resource (right hand scale) is zero. Of course this cannot happen in
real life because populations regulate their sizes by their longevity,
fecundity, disease and predation. Besides it costs more and more energy
to find the last left-overs of the resource, scattered here and there (this
is NOT the case for CO2).
The right-hand side plots (red) growth rate against resource use, showing
high growth rate at 100% and rapid decrease towards 0% (top). Note, however,
that each population and each species and each individual within a species
has its own growth curve. Note also that this graph has more value as a
thought experiment than reflecting the real-world situation.

For
populations of warm-blooded animals it is impossible to live near exhaustion
of their resources because they need so much energy even while sleeping.
But cold-blooded animals (insects, worms) do much better. Best of all do
the plants because they don't even move, building their biomass up gradually
while living long lives. They live from a different source of food, from
the energy of the sun which comes to them only at the cost of dehydration.
So they are able to live even in low levels of their most important resource,
CO2.
Note that CO2 in air is rare. Whereas one in five molecules is oxygen,
only one in 3000 is CO2. It is a miracle that plants do so well in such
a depleted resource. But CO2 was once six times richer in the age of the
dinosaurs (2000ppmv), while the climate was also warmer. Now that the concentration
of CO2 is increasing again, we see plants doing well, expected to grow
exponentially (ever faster) in reaction to CO2 (see diagram).

This could explain why we observe a linear increase of CO2 associated
with an exponential sequestrationtion of exponential anthropogenic (man-made)
CO2 from an exponential growth of plants. Ironically the modern plants
(herbs, weeds, leafy trees, grasses) react with less vigour (20-40% for
a doubling of CO2) than the ancient types (ferns, cycads, pine trees) (80-100%
for a doubling in CO2) because they have better photosynthesis evolved
in a low carbondioxide world and are therefore not starved as much. Note
that growth is possible only if a plant's other resources are adequate:
warmth + water + nutrients, which explains why natural carbon sequestration
happens only in certain regions of the planet.
Note that CO2 is perhaps
the only scarce resource that is not scattered around, but is instead spread
very evenly through the atmosphere.
~~~
If our discovery of a direct path for CO2 from symbiotic
decomposition to the plant's roots is valid, then 50% or more of a
plant's CO2 needs could come direct from the soil, and this has been overlooked
by agriculturalists and scientists. Experiments with higher CO2 concentrations
in air have also excluded this source of raised CO2 in soil. Perhaps a
time delay is in place for the path: CO2 in air => more
plant growth => more leaf drop => more decomposition
=> more CO2 uptake from the soil. For this reason, natural ecosystems
may sequester CO2 better than experiments suggest.We discovered that decomposition cannot complete for
lack of energy. Plants therefore secrete energy (sugars) from their roots
to promote complete and fast decomposition (symbiotic decomposition).
For a small expenditure in sugars, they receive the nutrients they crave
for, and also all CO2 that goes with it. Scientists have indeed
observed that plant roots excrete sugars, and so do marine algae and plankton,
as well as coral reefs. However, they have not (yet) discovered why. See
our
DDA chapter.~~~
The way molecules move in air is radically different from how they
move in water. In a liquid, the molecules are packed closely together,
with enough freedom to slide past one another, whereas in air (which is
800 times less dense), they move freely with a large amount of vacuum in
between. In this vacuum the gas molecules attain high velocities, allowing
them to mix rapidly. Ironically, each type of molecule (O2, N2, CO2) behaves
as if the others don't exist, their individual partial pressures being
in balance with those in water, earth, leaves and so on. One would be tempted
to treat the atmosphere as a reservoir for each constituent gas,
and this is indeed how scientists treat it. The idea of a pipe is
therefore new, requiring some explanation.

The amount of CO2 in air is very small (0.03%), much like that of a pipe
compared to a reservoir (100%).

An increase in (partial) pressure results in an increase of plant
growth which results in an increase in gas exchange (flow).

In a dead world, CO2 concentrations would be in perfect equilibrium between
air, sea and land. However, a living world pumps it around, absorbing
it into plant life and exhaling it again from animal life and decomposition
while also reacting to global temperature, sunshine and CO2 concentration
changes.

Depending on changes in temperature, sea and land act as reservoirs (1800Gt
and 38,000Gt) connected by a narrow pipe (700Gt) with a high throughput
(200Gt/y). When the earth and the sea warm up, CO2 is released and absorbed
by land life. When the earth cools, the reverse takes place.

High volume pipes exist but are ignored by atmospheric scientists
because they do not connect through air, even though they store much carbon
(see diagram below).

The rate of transport through the pipe is given by how long the
gas stays inside. It is interesting therefore to note that estimates for
the residence time of CO2 in air, vary between 2 and 100 years, with 5
perhaps as closest estimate (3 years in the block diagram above). The reasons
for this wide range of uncertainty are:

some measurements rely on radioactive carbon (made from nitrogen by high
energy radiation). However, the air is polluted by man-made CO2 which has
no radioactive carbon (because it sat underground and lost it over time),
and by nuclear tests which cause high concentrations of it. To make matters
worse, the production of radioactive carbon is not constant. Nuclear 14-C
indeed had a residence time of about 5 years.

one method relies on the dilution of radioactive carbon by man-made carbon,
assuming that we know the precise origin, quantity and decay of each and
the role the oceans play in this.

all methods assume that CO2 is evenly spread through the atmosphere and
that it cycles equally fast in all atmospheric layers, which is unlikely.

alll methods assume a single 'average' cycle, however nature is bound to
have both very fast and very slow cycles (see diagram below).

all methods assume a dead planet where life does not react to concentrations
in CO2 or temperature, and does not influence the flow rate.

the methods used cannot detect fast cycles, as these return the same carbon
that was absorbed a short time before.

some CO2 dissolves rapidly in rain and is washed out of the air in a matter
of days.

Main
carbon pathways on land and in the seaThe diagram shows how an imaginary carbon pipe connects all living
creatures and also to some extent with the inanimate sea water into which
CO2 dissolves so easily. As can be seen, the highest flow is found outside
the atmosphere, inside the soil on land and the photic (sun-lit) zone in
the sea. CO2 escaping direct from the soil is also likely to be trapped
first by the overlying canopy, resulting in a residence time of hours rather
than years. Although leaf litter and animal wastes take months to recycle,
the residence time here is still a fraction of a year.
The sea circulates faster still: because plankton cells are so small,
growth rates in the sea are extraordinarily high. For instance, the rise
and fall of a plankton bloom can happen within a week, and dead plankton
fully recycled within a month (most of which is returned within a week),
resulting in a residence time of less than one month rather than 5 years.
But recycling with the deep sea bottom takes hundreds of years. Likewise,
the CO2 found in the upper atmosphere is not likely to play a role, resulting
in long residence times. It is therefore wrong to think of an 'average'
residence time in air.

To accentuate the confusion, scientists think that
the residual CO2 in air, amounting to 2Gt/y of the 6Gt/y that humans
emit, can decay only at the rate that it was accrued, which could take
a century once the 600ppm is reached (a doubling of CO2).

talking of 'average residence time' of CO2
in air is nonsense

When oceans expel CO2 as they warm up, the new CO2 charges the carbon
pipe, resulting in faster turnover in coastal seas and on land where vegetation
is not severely limited by other factors. The human CO2 also charges the
carbon pipe.

November
2009: a study by Wolfgang KnorrScientists at the University
of Bristol found that over a long time period from 1850 to present, the
ratio between CO2 in air and the amount sequestered by land and sea vegetation
has remained remarkably constant to within 1%, despite a significant rise
in human-produced CO2. In other words, as the concentration in air rises,
so does the rate of recycling. This study essentially supports what we
have explained above.

Reader please note that some of this we discovered here
at Seafriends in 2005, as explained in the DDA
chapter. The planktonic decomposers and the way symbiotic decomposition
transfers CO2 direct to the plant as a significant source of carbon dioxide,
is a discovery that has not (yet) been confirmed by mainstream science.

Is the level of carbon
dioxide in air rising?The
diagram shows the growth in population and our use of resources. The vertical
scale is logarithmic, which shows exponential growth best. In the top left
one sees three lines for a 5,10 and 100 times growth rate per century.
It brings the shocking reality that population (p) still grows at the rate
of 10x per century, all energy use (e) at close to 100x per century. Ironically,
the top brown curve for CO2 (h) does not keep up with these trends, and
by comparison, appears to be levelling off. In other words, the
relationship between increased CO2 levels in air, and the growing use of
energy, is rather weak. Then again, a doubling in 30 years would
imply an underlying growth rate of close to ten times per century, still
far removed from the actual rate of increase in fossil fuel burning. Reader,
note that in climate chapter 4, a strong relation
between CO2 in air and human emisions is defended.
Note also that the world is still doing relatively well, as measured
by GDP per person (gp), and even the use of water per person is still climbing,
but not for long (wp). An interesting fact is that the total energy (e)
until 1800 consisted of burning biomass (sustainable). In 1800 the use
of coal took off, later flattening off (b) because by 1870 oil replaced
it and later still, gas.

A high CO2 world

There is a lot of panic about CO2 levels rising to 400ppm and above, but
in the history of the planet, CO2 has often been much higher, and the present
low levels of CO2 could be considered an anomaly. At the time of the great
dinosaurs, carbon dioxide levels were five times higher still (2000ppm)
and life as we know, was prolific back then. Evolution towards diversity
also thrived.It is further important to note how much volcanism contributed
to CO2 and that current low concentrations are an anomaly.The world did
very well back then. No reason to panic!The work of Budyko has been replicated and refined, and essentially
been confirmed, see diagram and further below.
To understand ancient epochs, read our Geologic
Timetable.

The
general consensus is that the concentration of CO2 in the atmosphere is
increasing. Very accurate measurements at mount Mauna Loa in Hawaii and
independently at Baring Head in New Zealand, show a steadily growing CO2
concentration (red line) [see
note2
below]. But the data before 1960 remains sketchy. The IPCC attaches
high value to CO2 measurements from air bubbles trapped in ice which indicated
that the pre-industrial concentration was about 270ppm. Knowing the age
of each point by the year rings in the ice, the brown curve resulted from
the Siple Dome in West Antarctica (drilling 1996-2005, 990m deep). However,
this curve did not join up with that of Mauna Loa, so it was arbitrarily
shifted right by 83 years, and also down a little. The reason for doing
so is that the first part of the core, containing compressed snow or firn,
is still 'open' to atmospheric influences, see dotted brown curve with
question marks, and the box below.

The ice core data is not a year by year measurement for each depth. It
is measurements of a range of layers, which are not linearly connected.
They then construct a CO2 average for each year. This means that each year
of data points is not a measurement; it’s a calculation of disjointed averages.
Hence any year over year specific changes in CO2 will be lost. Note also
that the Keeling curve for Mauna Loa is based on minimum CO2 values,
and that ice cores enclose average CO2 values.

Some scientists [Jaworowsky, Segalstad] mention that the method is flawed,
since CO2 does dissolve into ice and it even escapes. For instance, the
starting pressure at the top of the curve is already 5 bar and increases
to 15 bar at the bottom.
Already since about 1750, chemistry scientists have done CO2 measurements
in a more classical way, and the tens of thousands of data points join
up quite well (green curve), even though many measurements were taken in
industrial cities. The green curve shows that perhaps the CO2 concentration
was not all that ideal both inside the industrial age and before. Note
how it eventually joined up with Mauna Loa.

Is
the 83 year shift scientifically acceptable?In the Siple Dome ice core
the age of each point in the core was accurately known from the core's
'year rings'. At the top of the core, snow is gradually being compressed
until it becomes ice. During all that time, the air in the core is thought
to stay in contact with the air above, which causes CO2 to escape. But
why would CO2 escape from a lower concentration to a higher one? If there
still exists an air path to the open air, should CO2 not escape from the
air to a lower concentration, thereby lifting the resulting curve upward?
Clearly there remain too many unanswered questions about whether the measured
CO2 in trapped air bubbles indeed represents the CO2 concentrations of
the past. Most worrying is that the dotted brown curve is not published.
In fact, the raw data is not available.

CO2 glaciology depends on the following unproved
assumptions, which in fact, have been proved wrong
[Prof.
Zbigniew Jaworowski 1992; see also reference [1] below]:

No liquid phase occurs in the ice at mean annual temperatures below -24ºC

The way air is entrapped in ice is a mechanical process and does not differentiate
between gas components (fractionation)

The air inclusions represent the original atmospheric air composition

High pressure of the ice does not influence the makeup of entrapped gases
and does not dissolve CO2 into ice in the form of clathrates.

The age of gases in the air bubbles is much younger than the age of the
ice in which they are entrapped, ranging from decades to millennia.

Drilling the ice core does not pollute it

Relaxation of the ice core after its pressure drops from hundreds of bar
to one, does not influence its content by forming cracks. (one bar per
12 metre)

Prof Jaworowsky found that indeed CO2 gas dissolves
readily in ice under pressure, forming clathrates; drilling contaminates
cores with drilling fluid while forming cracks; as ice cores relax, dissolved
CO2 gas from clathrates expands and forms new bubbles; gas escapes from
ice cores (likewise for nitrogen and oxygen at different 'dissociation'
pressures); average pre-industrial CO2 concentration was around 330ppmv,
not 260.[1,6] [5] Another fact is that CO2 is 70 times more soluble in
water/ice than nitrogen and 30x more than oxygen.

How
CO2 disappears from ice cores; CO2 in Natural IceNatural ice contains approximately
100 ppm (by weight) of enclosed air. This air is mainly located in bubbles.
Carbon dioxide is an exception. The fraction of CO2 present in bubbles
was estimated to be only about 20%. The remaining part is dissolved in
the ice. Measurements of the CO2 content of ice samples from temperate
and cold glacier ice as well as of freshly fallen snow and of a laboratory-grown
single crystal were studied. It is probable that a local equilibrium is
reached between the CO2 dissolved in the ice and the CO2 of the surroundings
and of the air bubbles. The CO2 content of ancient air is directly preserved
neither in the total CO2 concentration nor in the CO2 concentration in
the bubbles. Possibly the CO2 content of ancient air may at least be estimated
if the solubility and the diffusion constant of CO2 in ice are known as
a function of temperature. (See also W79-09342) (Humphreys-ISWS)

One cannot deduce a past static state using
a dynamic conditions method.

Measurements of gases, temperature and volcanic activity are done by
measuring proxies, such as the amount of dust in a core for volcanic
activity, and the ratios of radioactive elements for temperature and carbon
dioxide. In all cases, a consistent record is obtained for the distant
past, but this never seems to join up with the situation of today and the
past two centuries. An inconvenient discontinuity remains. So we can't
be sure whether the proxies are right. The fact that the past does not
join up with the present, is in fact proof that there is something wrong.
If only the top of the ice core or sediment core would agree with today,
the methods would gain more credibility. So far, they don't.
The graph shown here illustrates the point: scientists (of the IPCC)
have abutted three different proxies to the reliable measurements of Mauna
Loa, without expressing doubt about the scientific validity of it. For
instance, has anyone tried to grow plants and seedlings at 180ppm? It suggests
that life on Earth during the ice ages was much less than half of what
we have today and very much less productive too.

Mauna Loa measurements
representative?The
CO2 measurements at Mauna Loa (Hawaii) and Baring Head (New Zealand) both
measure CO2 concentrations over the Pacific Ocean, the world's largest
ocean. As such they are representative only of CO2 above the ocean at their
respective latitudes, and will almost certainly not represent CO2 concentrations
found above land. This graph, plotting CO2 levels against wind speed is
not from Mauna Loa but from Diekirch, Luxemburg. Notice the wide spread
(320-560ppm) in CO2 levels. The red baseline is arbitrarily chosen to represent
'maximal atmospheric mixing'. We would have liked to see such a graph from
Mauna Loa [3] and also the original raw (unfiltered and uncorrected) data.
See notes [2] and [3] below. Apparently there are now some 100 CO2 monitoring
stations world-wide.Note the large amount of
uncertainty and thus scope for arbitrary 'adjustments' and fraud, because
it is politically unthinkable that the Keeling Curve one day may dip downward
steeply. Since 2008 the Keeling curve has been flattening and may begin
to dip soon as a result of cooling oceans. Who knows. See also climate
chapter4.

[1] Prof. Zbigniew Jaworowski: Climate Change: Incorrect
information on pre-industrial CO2. March 19, 2004. Statement of Prof.
Zbigniew Jaworowski, Chairman, Scientific Council of Central Laboratory
for Radiological Protection Warsaw, Poland. http://www.middlebury.net/op-ed/Jawoworski%20CO2%202004.doc[2] Note re Mauna Loa and Baring
Point: these two places also 'cherry-pick' their results from natural
variations in their measurements. At Mauna Loa the low points are selected
in order to avoid measuring CO2 from nearby volcanoes. Thus the wind direction
is important in their measurements, as it is also at Baring Point. Both
sites measure the CO2 concentration above the ocean, thus are not representative
of CO2 over land, or 'world average' CO2.[3] Ferdinand Engelbeen (Belgium) has a very good
page with data and graphs, studying whether the increase of CO2 is from
human sources and also the raw data of Mauna Loa, and much more: http://www.ferdinand-engelbeen.be/klimaat/co2_measurements.html
We agree, the human signature is found wherever CO2 is found or used, but
there is no hard proof that the rising level of CO2 in air is caused by
humans and that this causes a rise in temperature. The noise on the Mauna
Loa signal is about 4 ppm CO2. The noise in the picture above is over 200ppm,
so we are skeptical about the ML noise of only 4ppm.[4] Fred Goldberg (2010?): Rate of increasing concentrations
of atmospheric carbon dioxide controlled by natural temperature variations
, looks at the only reliable data, yearly human emissions and yearly CO2
increases as per Mauna Loa, and concludes that temperature variations come
from elsewhere (ENSO, volcanoes) and this drives the level of CO2 emitted
or absorbed by the oceans. There is no human signature. www.heartland.org/custom/semod_policybot/pdf/25543.pdf[5] www.ferdinand-engelbeen.be/klimaat/jaworowski.html
Ferdinand Engelbeen rebuts Jaworoski's criticism. The science is not settled.[6] www.21stcenturysciencetech.com/2006_articles/IceCoreSprg97.pdf
Zbigniew Jaworowski (1997): Ice Core Data Show No Carbon Dioxide Increase.
Jaworowski explains in detail what is going on in ice as it ages under
pressure in ice sheets.

Where is the CO2 in the
oceans?

There is a difference between CO2 from burning wood and that from fossil
fuels in the amount of radioactive carbon. Weak cosmic rays are capable
of changing a normal nitrogen atom into radioactive carbon. So a very small
percentage of the air we breathe is radioactive. When plants incorporate
this CO2 into their woody tissues, it is locked in place while its radioactivity
slowly decays to zero. On the basis of this, scientists are able to measure
the date of anything that has been made by life. However, in the course
of millions of years, the remaining radioactivity can no longer be determined,
as in fossil coal and oil. CO2 from burning coal is thus entirely non-radioactive.

With great difficulty the amount of fossil CO2 can be calculated from
the total CO2 encountered:

the amount of non-radioactive CO2 is large, and that of the radioactive
part is small.

only a very small amount of non-radioactive CO2 originated from fossil
fuel.

one cannot tell from the reduced radioactivity whether this was caused
by age or by dispersion into the rest of the ocean which is also rather
old, or by the amount of human-made CO2.

In the diagrams above, the result is shown of how much CO2 in the ocean
is likely to have occurred from fossil fuel. Apart from a mixing area in
the South Atlantic, the ocean remains essentially layered to some 1000m
(because of thermoclines). The red band corresponds to 60-70µmol/kg
of fossil CO2 compared to a total of 2050µmol/kg, or about 3%. So
the whole effect of the industrial age boils down to an increase of 3%
fossil CO2 in the surface of the ocean. Note that this does not mean that
the sea is sequestering CO2 from the atmosphere. It just means that in
the exchange between ocean and atmosphere, fossil CO2 takes part, as expected.

The question now remains whether this CO2 caused the oceans to become
more acidic. But first we need to know how acidic the oceans normally are.

How much CO2 is absorbed by
the oceans?We
have rough estimates of how much carbon dioxide is recycled by the oceans
(40-100GtC/y), but no hard data as to how much is permanently absorbed
by it. The whole question about whether CO2 causes global warming or global
warming causing CO2 has not been solved either. With nearly 40,000 GtC
in the oceans, of which about half would escape for 10 degrees warming,
means that a very small warming of 0.1 degree would still release 200 GtC
to the air, or 25 years of human consumption. Global warming protagonists
insist that more warming has happened than that, since the industrial revolution.

From sediment cores, scientists were able to obtain a record of past
carbon dioxide levels, and these were very high for about 200 million years,
with some 50 million years of low levels, and earlier still, very high
indeed. So where did all that carbon come from and where did it go to?
From the blue line one can see clearly two sequestration periods, one
in the Carbon/Devonian 350-400 million years ago, and this was when coal
was laid down in the freshwater marshes (a vast quantity). During the dip
at the end of the Cretacious (K), all oil was laid down in the middle seas
while Gondwana was breaking up. Presumably all this CO2 came from volcanic
activity.

It is important to remember that in order for the oceans to permanently
fix more CO2 (which is true also for plants on land), the level of CO2
in the air needs to be higher than it was before the industrial revolution
(the
hockey stick for global temperatures). Sequestration at
previous CO2 levels is not possible.

It is widely claimed that the oceans absorb (sequester) up to 30% of
anthropogenic (man-made) CO2, but this cannot be measured.

Ocean
CO2 sinks and sources

The Joint Global Ocean Flux
(JGOFS) survey has substaniated that the oceans absorb CO2 in cold seas
while expelling it in warm seas, as shown in the above map. Although much
of it (if not all) can be attributed to the fact that CO2 dissolves better
in cold water, which can also contain more of it, there is also the biological
pump. The sea is an ecosystem in which phytoplankton absorb CO2 as
the beginning of the food chain which ends in top predators. When they
die, they sink to the bottom, thus continually pumping CO2 towards
the bottom of the oceans. In ocean upwellings, some of this CO2 reappears
at the surface. There are two areas of high productivity: the southern
oceans and the equator, but the one is a source, as the other is a sink
for CO2. So the ocean pump draws CO2 down in cold seas while expelling
it in warm seas. Reader please note that it cannot be ascertained whether
the oceans as a whole absorb or emit CO2.

The
seasonal greening of Earth

Satellite scans from NASA show
seasonal changes in the chlorophyll greenness of land and sea. In the northern
summer the ice and snow covering the boreal conifer forests has melted,
and the deciduous trees of temperate climates have sprung into leaf. It
is a massive change from winter. By comparison, the southern hemisphere
in its summer, does not have much change to show for, mainly due to the
fact that there is little temperate and boreal land, but the Southern Ocean
does spring into bloom. From just over one decade of observations, it was
calculated that Earth's greening increased about 6% or about 0.5% per year,
mainly at the fringes of forests. These maps cannot show that forests also
become denser. However, 0.5% of 70Gt living plant matter = 0.35Gt, compared
to 8Gt human emissions. Note that sequestration by plants can occur only
in places with enough moisture and nutrients.

How acidic are the oceans?As
this map suggests, ocean pH measurements have been done all over the world
and in the most unlikely places. The false colour scale on the right suggests
a range from 7.9 to 8.2 (personally I have measured a wider range from
7.8 to 8.3). The lowest pH occurs in upwelling areas whereas highest pH
occurs in the centres of ocean gyres. From this extensive mix it would
be difficult to state what the 'average' pH is for the oceans, let alone
whether the oceans have become more or less acidic. Note that upwelling
areas are more acidic because high-CO2 bottom water surfaces, warms up
and makes CO2 more readily available, a bonus for photosynthesis by marine
plankton.

My own measurements (see DDA) showed
that the resulting pH is a tug-of-war between photosynthesisers that scavenge
hydrogen ions to such extent that some lakes in summer and rock pools can
go as high as 9.0, against decomposers that decompose living and nonliving
biomatter to unlikely levels of 5.0 in putrid mud. pH is relatively low
in eutrophied (overnourished) seas that can only be called sick. This implies
that the degrading state of our coastal seas must have been accompanied
by a decrease in pH ('acidification'). However, none of the scientific
papers I read even mentioned this.Also, in order to measure the 'natural'
pH in a sample, onne must first kill all living organisms (phytoplankton
and bacteria). however, this is never done.

Where does the scare story come from?The
article by Feely et al [1.] begins with unsubstantiated assertions, showing
the researchers' bias: Global warming is increasing
ocean temperatures and raising sea levels. New scientific research shows
that our oceans are facing yet another threat due to global-warming-
related emissions. Their basic chemistry is changing because of the uptake
of carbon dioxide released by human activities. "The pH of our ocean
surface waters has already fallen by about 0.1 units from about 8.16 to
8.05 since the beginning of the Industrial Revolution, around 200 years
ago and it may fall as much by 0.4 units by 2100." - These 'scientists' use a computer model for the
uptake of CO2 from air, assuming that consumption and emissions will increase
exponentially from zero in 1850. The resulting pH curve is then shifted
up/down to co-incide with today's assumed value of 8.05, suggesting an
initial pH of 8.15 (that was never measured experimentally) and thus 'already'
a drop in pH of 0.1 since 'before the industrial revolution' (pink
rectangle). [sigh] Another misleading
and untested computer simulation.

Acidity variation in the South China SeaResearchers
[1] used the radioactive Boron-11 isotope in fossil corals to reconstruct
a Holocene history of sea surface pH variations for the South China Sea.
It showed that alkalinity varied between a pH of 7.91 and 8.29 during the
past seven thousand years. Such variability far overshadows the fear of
0.3 pH change in two centuries. It must be noted, however, that most of
the variation was towards 'healthier' values above 8.2.

Are oceans becoming more
acidic?Measurements done during two NOAA voyages in the Pacific, about a decade
apart, are the cause of the whole ruckus about ocean acidification. From
these two voyages (one experiment) it is claimed that the average alkalinity
of the ocean decreased by just 0.025 pH
units amounting to an increase in DIC (CO2) of 15µmol/kg (0.73% of
a total of 2050µmol/kg). I have not been able to ascertain whether
adequate precautions have been followed, because measuring an absolute
difference of 0.1pH borders on the margins of the possible, let alone 0.01.
In the decade between the two voyages, also the pH measuring apparatus
has changed, and so on. But a pH unit of 0.025 on a rather exponential
(logarithmic scale) amounts to antilog(-0.025)=0.944 or 5.6% more hydrogen
ions. Note that this is the only accurately measured value.

The Bermuda Atlantic Time-series Study (BATS)There
exist very few time series of ocean measurements. The longest are HOTS
(Hawaii Ocean Time Series, since 1990, does not measure pH) and BATS (Bermuda
Atlantic Time-series Study, since 1984). Shown here is BATS for twenty
years, with total dissolved inorganic carbon (DIC, mmol/kg), TA (Total
Alkalinity), CO2 concentration (ppmv) and pH. One can see that there is
quite a high degree of variability, with total carbon varying by 50mmol/kg
(1.4%), CO2 all over the place, varying 100ppmv (25%) and the pH by 0.12
(32% hydrogen ions). With some difficulty a slanting line can be drawn
for -0.03 pH (7%H) and +20ppm CO2 (5.9%) in 20 years. In the same period
Mauna Loa measured an increase from 345 to 375ppm (8.6%). Before one can
say that the decline in pH was caused by carbondioxide, one needs to prove
that it was not caused by other acid gases, land-based effluent and eutrophication/degradation
were not the cause. This has not been attempted.
Note that the time series does not show any cyclic effect from El Niño
(temperature variation) or any other cycle and is therefore too short to
draw any certain conclusions from. Note that the pH makes large excursions
that must have been caused by life. Note also that the pH makes large excursions
downward but not upward, as if it reaches a maximum. This agrees with our
observations that a high pH is limiting plankton growth: as plankton blooms
scavenge hydrogen ions (and CO2 which is practically a mirror image), which
causes the pH to rise until a dearth of (lack of) hydrogen ions becomes
limiting, while there is still plenty of CO2 for photosynthesis (300-320ppm)!
It also shows that measuring pH without first disabling all life in the
sample, does not make much sense.

The Monterey Bay marine aquariums have been monitoring seawater
parameters (temperature, pH, salinity, ammonia, nitrite, nitrate, phosphorus)
for over a decade, and the graph here shows average monthly pH from 1995
to 2009. Because of the depth of the intake, near the thermocline, most
parameters fluctuate wildly between surface and deep water quality. In
a single day the temperature may vary regularly by 2ºC and sometimes
by 4ºC, considering that winter to summer varies by only 2-3ºC.Compare this to the oceanic BATS data above, and it becomes
clear that coastal water varies considerably from day to day, season to
season and year to year. The important message here
is, that when people talk about 'THE average pH' of THE ocean, they
do not know what they are talking about.

Reader please note that these are the ONLY
experimental
smoking guns for ocean acidification!

Those familiar with science know that a single experiment cannot be
hailed as conclusive, as it needs to be replicated by others, and also
shown to be true over a representative extent of ocean. But the situation
becomes worse, if one knows that an increase in hydrogen ions of pH=-0.1
also makes the sea 20% more productive, leading to 20% more biomass if
nutrients were sufficiently available. Such is the case in all coastal
seas above continental shelves and far beyond due to rampant soil erosion.

In 2003 a paper appeared by Caldeira & Wickett which is based on
computer simulations. They claim that already the oceans have acidified
by 0.1 pH units. No actual measurements to back this up, and no mention
of the calcium ion and carbonate buffering of sediments and no mention
of eutrophication either. The 0.1pH amounts to 21% more hydrogen ions.
This paper is interested in the possibility of injecting CO2 into the deep
sea, a technological 'solution' to reduce emissions.

In 2005 a paper by Jacobson appeared, who calculated pH from dissociation
constants, assuming that the ocean is in equilibrium with the air.
In his paper he includes dissociation constants of over 50 possible ion
species in seawater, a truly complex system with enough scope for error.
He claims that in 1751 ocean pH was 8.25 and now 8.14, a difference of
0.11 pH units or 22% more hydrogen ions. We wonder why the measurements
in 1751 were so accurate and reliable. He goes further by claiming that
when CO2 reaches 750ppm, the ocean will eventually settle at a pH=7.88,
or a drop of 0.37 or an increase in hydrogen ions('acidity') of nearly
60%.

Reader please note that around 1750 electricity was about to be invented
by Benjamin Franklin (see our timetable
of human inventions), and pH could be determined only by the method of
titration (litmus test?), and it is not possible to get more accurate than
0.2pH unit with this, regardless of the amount of sampling and averaging.
Even today it is difficult to guarantee this kind of absolute exactness,
considering the state of pH sensors and calibration buffers. In addition,
the pH of the sea changes night to day, from day to day and winter to summer
and from place to place. In fact, after our discoveries (DDA),
natural
alkalinity of the water can be established only after first disabling
all life in the sample, and this has never before been considered.
For
Jacobson to claim an average ocean pH of 8.25 in 1751 is rather naive,
if not fraudulent. His paper builds further on this by extrapolating:

Year

1751

2000

2100?

CO2 ppmv

275

375 (1.36x)

750 (2.73x)

pH of ocean

8.24691

8.13647 (1.29x H+)

7.87615 (2.35x H+)

Did he verify this with tests? No. The interacting chemistry of seawater
is just too complicated to fully understand and even the carbonate part
of it is not fully understood.
Although time series are still too short, other stations report increases
of 0.4 to 2.2 µmol/y, equating to a decrease in pH of around 0.0012
per year. Note that because pH is a logarithmic scale, this annual decrease
cannot be extended far into the future by multiplying it with the number
of years.

The Bjerrum plot of the
carbonate systemMuch
ado is being made of the Bjerrum Plot, named after N Bjerrum (1914) who
invented the diagram for visually representing the equilibrium between
the three carbonate species CO2, HCO3 and CO3. With very precise equations,
corrected for temperature, this system is well defined for the ideal situation
(distilled water). What the plot says, is that for instance at a pH of
8.1 for the ocean, the three carbonate species are given by the intersection
of the dashed vertical with each of the curves, giving 0.02, 2.05 and 0.12
mmol/kg for each (note that the drawing above is not accurate). By making
the sample more acidic, hydrogen ions out-compete the hydroxyl ions, which
results in more CO2 in solution, less CO3 and an inconsequential change
in HCO3 (the FAT arrows). No problems here, but scientists now claim that
an increase in CO2 is the same, and this cannot be true as an increase
in CO2 simply lifts all three curves a little higher (Le Chatelier's principle).
Note the relative concentrations CO2 : HCO3 : CO3 = 0.02 : 2.05 : 0.12
= 1 : 100 : 6

Le
Chatelier's Principle: Adding CO2 to a CO2/carbonate equilibrium (including
carbonate rock) will drive the reaction towards the formation of MORE
carbonates, not less.

But there is more wrong:

the plot doesn't explain the difference in pH between rain
water, lakes and seas.
Neither does it explain the wide range in the pH of lakes.

the plot does not take account of other mineral ions, of which calcium
is the most important. These ions compete for hydrogen or hydroxyl ions
and even for ions of the carbonate system.

the plot does not include stabilising carbonate deposits.

the plot has never been proved experimentally for the complex sea water
system.

what the Bjerrum plot DOES show is that if the sea becomes acidic for other
reasons than CO2 (acid rain, runoff, eutrophication, warming, artificial
addition of acids), CO2 levels WILL increase even if atmospheric CO2 does
not increase.

Rather than computer simulations we like to see an experimental plot with
the amount of CO2 horizontally, and vertically the three carbonate species
and pH. Failing this, the Bjerrum plot is merely interesting item and of
little consequence to the issue of ocean acidification. Below is a more
exact graphical representation of the relationships between CO2, CO3 ion
and pH, according to the Bjerrum plot. It shows the effect of adding an
acid (HCl) to lower the pH or a lye (NaOH) to raise pH, but it is not representative
of the natural situation in the real world. Note also that the graph disagrees
with the concentrations quoted in the Bjerrum plot above, as it also disagrees
with how CO2 dissolves in water (above).

Fraudulent
CO2 science, scientific CO2 fraudDoing experiments in the
ocean that truly reflect the real-world situation is difficult if not impossible.
So scientists take shortcuts, essentially in two ways:

they add hydrochloric acid (HCl,
because salt water has a lot of chloride ions already). This shifts the
pH baseline in the Bjerrum plot above to the right, producing more CO2
in a more acidic environment. It is a scientific fraud because it also
produces
less of the CO3 ion instead of more, resulting in
abnormal dissolution of shell.

they bubble CO2 through the
water, thereby essentially increasing the left-hand side of the equilibrium
equation. Although this reflects the real-world more than trickling acids
through the water, it is still a scientific fraud because the water is
not given time to form more of the CO3 ion from carbonate deposits.

In all experiments the enriched
water is flowed through the experiment, never giving enough time for an
equilibrium with the calcium-rich environment which increases CO3. In other
words, the experiment does not allow the water to buffer the enriched water.
Neither method reflects the real-world situation, and this is scientific
fraud.

"..
coral calcification responds to [the concentration of the CO3 ion] rather
than pH or some other component of the surrounding seawater environment"
(Langdon 2002, Schneider & Erez 2006) ".. lending support to the hypothesis
that it is the product of [Ca ion concentration] and [CO3 ion concentration]
but since Ca is not limiting, calcification is mainly dependent on the
[CO3 ion concentration]" - in Kleypas et al (2006).
Reader, this essentially supports the above.

Does calcification release
CO2?Some publications insist
that during the formation of limestone (calcification), CO2 is produced
rather than absorbed, as if saying that the coral reefs that consist almost
completely of CaCO3, do not contain CO2, and that they were built by releasing
CO2. As if trees by forming wood, release CO2 rather than sequester it.
So what is the story?We know that trees sequester
(absorb) CO2 to make woody tissues, and when these decay, the CO2 is returned
to the air. But when the trees fall in marshes, decompositon stops and
the CO2 remains captured, eventually turning into coal and gas. Is the
same not happening on coral reefs? The story here is considerably more
complicated and uncertain.According to the equilibrium
equation and the graph above, one can see that taking 50 µmol CO3
out (green), about 8 µmol of CO2 (orange) will escape from solution
(1/6). Some scientists insist that even more will escape (Zondervan et
al. 2001) because it takes two molecules of CO2 to produce one CO3 ion.
It may be worse still because of the 1:100:6 ratios where one CO3 ion may
shift 100/6 ions of HCO3 towards CO2. The problem here is the
calcium ion Ca2+ of which some is in equilibrium with
the CO32- ion and this in turn is in equilibrium with sediments,
largely made up of limestone CaCO3. When one studies salt water in a laboratory
beaker, it is true that calcification leads to the release of CO2. Likewise
in a marine aquarium, a seashell can make new shell only when somewhere
else a shell dissolves. Thus the path to the coral reef comes from sediments:

CaCO3 in sediment
=> Ca2+ + CO32- in
sea water => CaCO3 in coral

without either release of CO2
or sequestration of it from air. Obviously, there is a lot of uncertainty
here.

Is phytoplankton
in decline?There have been alarming claims that the phytoplankton in the oceans
has declined by 40-60% during the period of global warming, pointing at
either temperature or CO2 to blame. Since phytoplankton forms the
food at the bottom of the food chain, it follows that all other marine
organisms, including fish are threatened.

This image from NASA Earth Observatory shows how diatoms, the most nutricious
"grass" of the oceans, declined (green graph) against projected rising
CO2 concentrations (blue graph, not actual)[1]. One can immediately see
that it is fake because the green graph is actual data from supposedly
1850 to present whereas the blue graph extends to unrealistic concentrations
of 1100ppmv in a fantasy future (present is around 400).

So let's look
at actual observations from seafarers, collated and normalised by
Boyce et al (2011). This was a mammoth task because observations were dissimilar
(colour estimates, Secchi Disk measurements, chemical analyses, satellite
observations) while covering mainly ships' sea lanes, mostly in the north.
The dataset was then split over ocean areas ranging from the Arctic to
the Antarctic, here overlaid in a single graph. Indeed a general decline
is apparent from a peak around 1950. Most importantly,the Arctic
has highest productivity and the equatorial Pacific least., suggesting
a temperature effect. However, remember that the warm tropics have a pronounced
thermocline which prevents nutrient-rich cool deep water from surfacing.
Note also that the data is skewed towards the northern summer. For good
measure the ships-observations of sea surface temperature (SST) as reconstructed
from the Comprehensive Ocean Atmosphere Data Set (COADS) is shown here
in magenta. A correlation is not evident.

Reader please note that our existing
knowledge of plankton ecosystems is ruefully inadequate and may even
be wrong.

So why is acidification
considered a problem?This
brings us to some questionable science that was looking for an excuse (Victoria
Fabry in James C Orr et al. 2005). By examining certain shell forming plankton
species like pteropods (wing-foots, pelagic snails that swim with their
foot), it was found that some had minor damage to their shells. Apart from
being inconclusive, these results were then hailed as proof that higher
acidity in the sea would dissolve shells faster and that eventually the
snails would not be able to make their shells fast enough, and that this
would lead to extensive ecosystem changes and extinction of species. Also
coral reefs would dissolve and weaken and combined with global warming,
disappear from the face of the ocean. Oops.

Correct me from being wrong, but there is something very fishy here.
It is known that CO2 dissolved in rain water, makes it more acidic (pH=5.5-6),
thus capable of dissolving limestone at a very slow rate, which takes a
dripstone stalagmite thousands of years to grow a few kg.

CO2 + CaCO3 + H2O => 2(HCO3)- + 2Ca2+(note the one way reaction => because water is transported away)

So it is thought that more CO2 in ocean water would do the same. Apart
from the fact that a pH=6 has 100 times more hydrogen ions than a pH=8,
and does not seem to worry freshwater snails in lakes, sea water is almost
saturated with calcium (Ca).

Remember the CO2 equilibrium equations
that end in carbonate CO32- of 0.12 mmol/kg compared to that
of Ca2+ of 10.4 mmol/kg? This means that there is not enough
carbonate in the water to combine with the free calcium, and any increase
in CO2 would mean that laying down a limestone skeleton becomes easier
rather than more difficult. An increase in carbonate leads to calcification
of CaCO3, just the opposite of what is being claimed! In other words, the
vast store of calcium in the oceans has a buffering effect. Notice in this
respect also the way salts precipitate when making table salt from sea
water (/oceano/seawater.htm), with
CaCO3 the first to settle out, followed by gypsum CaSO4.

Sarma et al. (1971) reported an increase in alkalinity of about 11 µmol/kg
when DIC (CO2 species as Dissolved Inorganic Carbon) increased by about
20µmol/kg, which should create some inconvenient doubt.

Calcite and aragonite saturationThere is a vast discussion going on and many experiments focusing on
'aragonite saturation', meaning that normal sea water should be
in balance with the limestone in sea shells, oversaturated even. However,
in practice all sea shells dissolve back into sea water, which means that
the concept of aragonite saturation and calcite saturation
may live only in our minds. Here is what's behind this idea:

On
the surface of the ocean all dissolved gases are in balance with those
in air. But in the water, with the help of sunlight, plants produce oxygen
while consuming CO2. So oxygen concentrations are higher and carbon dioxide
concentrations lower than in air. As one goes deeper, the beneficial effect
of photosynthesis decreases, and CO2 increases due to breathing and decomposition.
In theory at least, the water becomes more acidic with depth, to the point
that the thin skeletons of plankton critters (coccolithophores, pteropods,
foraminifers, etc) could begin to dissolve. This is called the
aragonite
saturation horizon (0.5-2.5km). Below it, the shells dissolve, whereas
above it, they supposedly don't. As we have shown above, this is a dubious
concept (Sarma et al, 1971). There is likewise also a calcite saturation
horizon (1.5-5km). The concept 'explains' why clay deposits
without limestone occur deeper than those with limestone as carbonate
ooze.
The diagram shows actually measured values for the carbonate ion CO32-
versus depth (red line). Below 2km the concentration is rather static although
it decreases further with pressure. Where it crosses the (hypothetical)
aragonite saturation horizon, sea shells will be dissolved gradually, and
below where it crosses the calcite horizon, calcite will dissolve as well.
It is thought that increased CO2, and thus acidity is the cause of this.
Sadly actual pH is missing from this graph (why was it not measured or
published?).

These hypothetical horizons are very dependent on temperature and pressure:
the higher the pressure, the more readily calcite dissolves. Lower temperatures
also increase the solubility of the water, and temperature decreases with
depth. Hence it is not clear whether acidity or pressure or temperature
are the main drivers. For this reasons the cold oceans like the Southern
ocean are most likely to become under-saturated, one of the main
scares.

What must also be remembered that the act of dissolving CaCO3 (limestone)
into seawater also increases the pH. Thus the huge amount of ocean sediment
will neutralise any acidification. It is estimated that ocean sediments
amount to 30,000,000Gt carbon, a massive reservoir. But since most of it
is in the deepest parts of the oceans, it may take a millennium to become
effective.

An ilustration of the
problem in understanding ocean chemistry with modelsThe Royal Society UK (2005)
report gives a good example of reasoning gone wrong: "Marine organisms
that construct CaCO3 structures, such as shells, are dependent on the presence
of bicarbonate and carbonate forms of dissolved inorganic carbon. Once
formed, CaCO3 will dissolve back into the water unless the surrounding
seawater contains sufficiently high concentrations of carbonate ions (CO32-).
. . .The formation of CaCO3 leads to an increased CO2 concentration in
the water. This apparently counterintuitive behaviour arises because two
ions of bicarbonate (HCO3-) react with one ion of doubly charged
(Ca2+) to form one molecule of CaCO3, which leads to the release
of one molecule of CO2. . . . Under current conditions, for each molecule
of CO2 produced during calcification, about 0.6 molecules are released
. . . A decrease in calcification resulting from increased acidity would
. . decrease the total emission [of CO2] from the oceans . . (Zondervan
et al. 2001)" "To make these calcareous
structures, seawater has to be supersaturated with calcium and carbonate
ions to ensure that once formed, the CaCO3 does not dissolve.""For example if the deep
oceans start to become more acidic, some carbonate will be dissolved from
sediments. This process tends to buffer the chemistry of the seawater so
that pH changes are lessened."The report adds: "Essentially
this is an area of great uncertainty. This example is provided, in part
to highlight the complexity of the interactions between the chemical and
biological processes in the oceans."

Reader,
figure it out: The more carbon dioxide is absorbed by the oceans, the more
it produces ??? The three equilibrium equations: an increase in CO2 on
left decreases CO3 on right??? Water needs to be saturated with
CaCO3 in order to make shells? An organism's internal chemistry and buffering
plays no role? What's wrong with experimenting?

0708135: a smooth tiger shell (Maurea tigris) has
almost completely dissolved back into seawater, showing its spire made
from more dissolution-resistant nacre (mother-of-pearl). It took
just over a year from live animal to this stage.

f012810: after about 6 months the fragile shell of a paper
nautilus becomes too brittle to handle. In 12 months it has dissolved completely
in clear seawater. Aluminium cans dissolve in 5-10 years!

How much carbonate in
sediments interacts with the sea water?I haven't found a useful
figure for this, apart from 30 million Gt in marine sediments. But what
we know is that the surface of the ocean is about 360 million km2 (360E12
m2). Thus the sea bottom is similar in size. If only 20cm of the sea soil
is perturbed (dug over) by benthic organisms, this would amount to 0.2m3
per m2. If only one fifth of this is limestone, then a cautious estimate
would yield 0.01 tC/m2 and the whole active ocean floor 3.6E12 tC or about
4000 GtC. The coastal regions, estimated at 10% of the ocean surface, would
have at least 400 GtC in active contact with the sea water. In all, this
is a formidable factor to consider, particularly for the CO3 ion.

Is CO2 a potent fertiliser?For plants to grow, they need to assemble C, H and O approximately
in the ratio CH2O. For this they need water and CO2 and an external energy.
Nutrients are required in much smaller amounts. A sufficient temperature
is also required. What many people don't realise is that there is only
one pool of CO2 (in air) for which all plants on land and in the sea compete,
to the extent that they draw it down until it becomes a major limiting
factor for all. It stands to reason then, that CO2 'fertilisation' enhances
plant growth, and indeed this is very much the case on land, provided enough
water, nutrients and warmth are also available. That is why natural carbon
sequestration happens in certain areas on the planet and not in others.

But in the sea, the situation is different because there is already such
an abundant source of carbon dioxide. Here the availability of nutrients
is the most important factor. Researchers find less than 10% growth for
a 100% increase in CO2, but benthic algae (seaweeds) may become much more
productive (Kuebler et al., 1999). Reader please note that our discovery
of slush and symbiotic decomposition, means that algal cells
have a different way of obtaining nutrients and CO2, particularly in blue
seas with little phytoplankton and nutrients.

Our own discoveries (DDA) show that
the sea does not at all work as expected, and that marine plants (and corals)
depend more or less on symbiotic decomposition. We have shown that a lowering
of the pH is beneficial to overall productivity and biomass.

As far as measuring the effect of raised CO2 levels on marine animals,
the situation is complicated because CO2 rapidly becomes toxic, with symptoms
of depression of physiological functions, depressed metabolic rate + activity
+ growth, followed by a collapse in circulation. Remember that free CO2
amounts to only 1% of the total CO2 'bonded' to the water and that it takes
some time for equilibrium with the other CO2 species to happen. It is thus
too easy to overdose the free CO2 by increasing the CO2 in the air above.
In other words, it is nearly impossible to mimic the natural situation
truthfully in an experiment.

Are coral reefs threatened?Nearly all alarmist publications and organisations claim that global
warming is bad for corals, to such extent that they may be extinct by 2050.
So how could coral reefs be threatened?

coral bleaching: coral bleaching by which a coral loses its symbiotic
algae, may cause death. It is loosely linked to exceptional warm water.
In case the Earth warms further, there is a chance that corals may not
survive. But in most reported cases I investigated, the quality of the
seawater was visibly poor, indicating stress from water degradation..

rising seas: seas may rise so fast due to the expansion of the water
column and due to the melting of ice caps, that corals may not keep up.
They will end up in deeper, darker water, which could mean death or at
least a major ecological turmoil. However, corals thrive in shallow water.

ocean acidification: corals make their limestone skeletons from
the calcium and carbonate ions in the water. If higher CO2 levels in the
atmosphere cause the sea to become more acidic, they may no longer be able
to do so, while also their (dead) skeletons dissolve faster back into the
sea. Reefs may become a thing of the past.

We owe Dr Craig Idso a great deal of gratitude for his very datailed 81-page
report summarising factual science to the contrary [1].
Only a very knowledgable insider would be able pull this off. So here folllows
a summary of his findings:

coral bleaching: scientists discovered that corals are not picky
about the type of symbiotic alg (a dinoflagellate) they host, and
are capable of adopting temperature-hardier variants of symbiodinium
in a process named symbiont-shuffling. In fact, corals may have
some hardier variants already as part of their customary algal lodgers.
Once a coral recovers from bleaching, it proves to be hardier and not as
easily bleached. So coral reefs adapt in a matter of months to years. Corals
also respond favourably to warmer water by also growing faster (3-5% for
one degree Celsius).

rising seas: many reefs are already limited in their growth by falling
dry during spring low tides. Also fresh water floating on the surface,
limits their growth. Fossil cores have shown that reefs have kept up with
rising and falling seas during the ice ages and long before that. Most
corals grow much faster than the worst-case predicted rise in sea level.

ocean acidification: because corals are encapsulated by live tissue
within which the concentrations of minerals are controlled by the coral
polyp, they are not very sensitive to acids outside. However, since their
metabolism depends on that of their algal symbionts (who provide the food),
they react favourably to raised levels of CO2, also producing skeleton
faster. Warmth and CO2 work together, resulting in rapid growth, rather
than decay.

Natural CO2_ventsIn June 2008 an important paper appeared in the scientific journal
Nature
[1]. Rather than doing tests in the laboratory, these scientists
studied how life changes around natural CO2 vents in the sea. The advantage
of this method is that one studies a situation that has been in existence
for a long time, giving species time to adapt (? see box below) while also
revealing long-term effects. The disadvantage is that the situation does
not allow for a sufficiently 'controlled' experiment. They chose 'cool'
CO2 vents that produce no additional poisons like hydrogen sulfide. The
study centred along a small islet/pensinsula along the larger island of
Ischia, on Italy's west coast. The study shows that along a daily fluctuating
gradient from normal sea water (pH=8.14) to acidic water (pH=6.57), species
diversity suddenly drops at around pH=6.8 (about 20 times more acidic).
It affects mainly calcareous algae, sea urchins, limpets, grazing snails
and barnacles. What these have in common is that they produce limestone
houses. They also found that normal green algae suddenly increase once
the others have gone (their grazers). The conclusion at the end of the
article: "This opportunity to observe the tipping
points at which principal groups of marine organisms are affected
by lowered pH proves that, even without global
warming, the projected rise in atmospheric CO2 concentration is hazardous,
as ocean acidification will probably bring
about reductions in biodiversity and radically
alter ecosystems."

In the BBC report (http://news.bbc.co.uk/2/hi/science/nature/7437862.stm),
the following quote appears: "I can't count the number of times that
scientific talks end with 'responses have not yet been documented in the
field'," said Elliott Norse, president of the Marine Conservation Biology
Institute (MCBI), "This paper puts that to rest for several ecologically
important marine groups.""The reason that the oceans are becoming more acidic is because
of the CO2 emissions that we are producing from burning fossil fuels,"
observed Dr Turley, "Add CO2 to seawater and you get carbonic acid;
it's simple chemistry, and therefore certain.
This means that the only way of reducing the
future impact of ocean acidification is the urgent, substantial reduction
in CO2 emissions." - Oops, what is so simple about ocean chemistry?

However, we have some reservations about this work, since science is
not only about measuring a correlation between supposed effect and cause,
but also about proving that the correlation is not caused by anything else,
which is what these scientists omitted. The CO2 vents were found towards
the main coast and the coastal gradient extended outward from this coast
(co-inciding with an increase in pH). Along such a gradient one also finds
a change in water clarity, sediment deposition, shelter from waves (exposure),
and human influences like sewage and run-off. It was telling that the measurements
done at the northern side of the islet were not reported. Loss of biodiversity
accompanied with a loss of coralline algae, urchins, limpets and others,
can also be observed anywhere in the world in a gradient from an estuary
to an outlying promontory, which is essentially the situation at the location
of study. However, the fact that most changes happened within 25 metres,
suggests that they were indeed caused by CO2.
More important, down to a pH of 7.6 (4x more acidic), no measurable
effect was found and minor loss of biodiversity. Thus a doubling (pH=7.9)
or quadrupling (pH=7.6) of CO2 concentrations in the atmosphere is not
going to have any measurable effect on marine life. This was not mentioned
in the article. In fact, the conclusion above is somewhat at odds with
it.

Our main criticism with the study concerns the fact that water with
a pH of 6.0 contains over 100 times the natural amount of CO2, and this
is poisonous enough to kill almost all water-breathing organisms. The fact
that animals went from perfectly healthy to completely dead within 25 metres,
means that the study can in no way be assumed to have any relationship
to the real-world situation. Researchers claimed to have calculated 'tipping
points' for various organisms, but in this case one cannot meaningfully
calculate 'average' CO2 concentrations. To understand this, study the results
in the box below.

The graph shows the essence
of the study. From left to right the transect distance along the rocky
shore, moving landward towards the field of CO2 bubblers on right. In this
field the pH varies considerably between 6.0 and 7.5 (30-fold). Note that
the gas was nearly pure CO2, capable of acidifying the water locally 1000-fold
to a pH of 5. However, mixing through turbulence, currents and waves soon
dilutes the acid, even though an area of over 50m remains consistently
highly acidic. Within a distance of a mere 25m, average acidity changes
from 6.5 to 7.7, accompanied by a critical change in the environment, affecting
in particular grazing sea urchins, snails and limpets. In their absence
while fed by higher CO2 levels, non-calcareous (edible) algae multiply.
The early decline of calcareous algae may not be entirely due to CO2 but
also to competition with the edible algae and normal coastal degradation.The problem with this study
is that it does not reflect a real-world situation where CO2 levels rise
slowly, evenly spread over all oceans. This study looks more like a local
CO2 Chernobyl with fatal fall-out wafting unpredictably here
and there, such that it becomes meaningless to talk of average pH. Note
that humans die at a 50-fold increase in CO2, and the situation here comes
pretty close to this, if not far worse.For instance, what is the
average
between 1 and 100? Is it 50? 10? 90? It depends on what the numbers mean
(weighted). If the numbers mean food, then the average lies close
to one, because hunger (=no food) kills. If the numbers mean threat, then
the average lies close to 100, because threats kill. It is also important to
note that nature is affected more by bad times than by good times, because
during bad times, one is more likely to die. Thus a killer cloud
of pH 6.2 wafting over, can be quite decisive, even though it may happen
sporadically, not affecting the average. Particularly affected are
the young (recruits) of all species. But the long-lived creatures are disadvantaged
more than the short-lived ones. It so happens that many of the long-lived
ones live in limestone houses. See also our chapter on
the principles of degradation.

Will the environment
adapt?As far as organisms are
capable of learning to avoid a killer cloud by migrating away, closing
up, burrowing and so, they are capable of adapting somewhat. But adaptation
by natural selection of the fittest is not possible because the vents are
not isolated like an island where the offspring are born near their surviving
parents. In the sea where everything is connected, and larvae drift vast
distances, the young of others are born near the vents whereas the offspring
of the survivors is born far away in normal conditions. Survivor genes
disappear or are diluted. Adaptation(evolution) in the sea differs
considerably from that on land.

Phytoplankton
calcification in a high-CO2 worldAn important and complicated study looked at the plankton record in
a deep sea core of the North Atlantic while also conducting experiments
with living cultures of one of the most common small phytoplankton organisms,
the coccolith Emiliania huxleyi. This coccolith is a major contributor
to calcium deposits in the oceans (50%). Contrary to other studies that
found a decrease in calcification, this study found an increase
in calcification, accompanied by larger individuals, although at somewhat
slower growth rates. The difference in experimental setup may have been
decisive: whereas others changed the pH by adding external acids or bases,
this team mimicked the real world more accurately by bubbling air with
known concentrations of CO2 (280-750ppm, pH=8.1-7.7) through their cultures.
This gives high credibility to their findings:

a doubling of particulate organic carbon, a doubling of size and calcite
shell

the deep cores showed an increase in coccolith mass of about 40% in the
past 220 years, which roughly agrees with experiments. The curve has a
hockey-stick appearance, climbing more steeply in the past 25 years (~25%).

This study shows that paradoxically, even though calcite dissolves more
rapidly at higher carbondioxide concentrations, it is apparently also more
easily made, resulting in heavier shells. A lower pH also encourages
productivity, which provides the energy to grow bigger and to make larger
shells. Note that this is exactly what we predicted
earlier and confirmed in our own measurements (see DDA).
The deep sea cores furthermore show that coccoliths provide a substantial
sink for CO2, while adjusting to high-CO2 conditions by increasing this
sink.
Please note that studies like this and others need to be replicated
and confirmed, and also note that the carbon chemistry of the oceans interacts
with stabilising sediments (buffer). Also note that sea temperature plays
an important role. Note also that even though the pH outside organisms
changes, this does not imply that it also changes INSIDE them. Important
to remember is that this study is about minute plants that benefit from
raised CO2 levels. For water-breathing animals, the situation may be
different.

The
graph shown here illustrates how coccolith mass was derived from deep sea
core RAPID 21-12-B, dating back to before 1800. Also shown is the IPCC
curve for CO2 concentrations in the atmosphere. The past 25 years of coccolith
growth suggests that it follows the rapid increase in CO2 concentration
in air. For a 20% increase in CO2, size increased about 30%. In laboratory
experiments, however, coccolith size and calcification increased mainly
betwen 400 and 600 ppm CO2, which has not happened in the sea yet. Could
temperature be a driving factor?

Another
study appeared, supporting increased calcification in higher CO2 concentrations"Co lead-author, Dr M Debora
Iglesias-Rodriguez, of the University of Southampton's School of Ocean
and Earth Science at the National Oceanography Centre, Southampton said:'This
work contradicts previous findings and shows, for the first time, that
calcification by phytoplankton could double by the end of this century.
This is important because the majority of ocean calcification is carried
out by coccolithophores such as Emiliania huxleyi and the amount of calcium
carbonate produced at the ocean surface is known to have a direct influence
on levels of atmospheric carbon dioxide.'

Previously,
the fact that carbon dioxide made the oceans more acidic was thought to
be harmful to all organisms that produce calcium carbonate - for example,
corals and coccolithophores (a group of calcium carbonate-producing phytoplankton).
However, observations in the laboratory and the deep ocean have shown that
the calcification of coccolithophores increases significantly with rising
carbon dioxide (CO2) levels, produced by human activity.

When CO2 enters the ocean
by gas exchange between water and the overlying air most of it is rapidly
converted to carbonic acid (H2CO3 ) which then forms bicarbonate (HCO3)
and carbonate (CO32-) ions. These reactions release hydrogen
ions (H+), making the water relatively more acidic.

When coccolithophores make
plates of calcium carbonate they also release carbon dioxide.(Coccolithophores
are a group of tiny marine plants which include Emiliania huxleyi,
they are extremely widespread.) But because these organisms photosynthesize
they also consume CO2. It is the balance between calcification - which
produces carbon dioxide - and the consumption of CO2 by photosynthesis
that will determine whether coccolithophores act as a "sink" (absorbing
CO2) or as a source of CO2 to the atmosphere. These
results, based on experiments that directly replicate how the oceans take
up carbon dioxide, show that the rise in CO2 produced by increased calcification
is mitigated by its removal through increased photosynthesis, with a
net effect that is unlikely to either contribute greatly or significantly
reduce the rise in atmospheric CO2.

Co-lead author, PhD student
Paul Halloran based at the Department of Earth Sciences, University of
Oxford said:'Our research has also revealed that, over the past 220 years,
coccolithophores have increased the mass of calcium carbonate they each
produce by around 40 per cent. These results are in agreement with previous
observations that coccolithophores are abundant through past periods of
ocean acidification such as 55 million years ago - the Paleocene Eocene
Thermal Maximum."

Owing to anthropogenic emissions, atmospheric
concentrations of carbon dioxide could almost double between 2006 and 2100
according to business-as-usual carbon dioxide emission scenarios. Because
the ocean absorbs carbon dioxide from the atmosphere, increasing atmospheric
carbon dioxide concentrations will lead to increasing dissolved inorganic
carbon and carbon dioxide in surface ocean waters, and hence acidification
and lower carbonate saturation states. As a consequence, it has been suggested
that marine calcifying organisms, for example corals, coralline algae,
molluscs and foraminifera, will have difficulties producing their skeletons
and shells at current rates, with potentially severe implications for marine
ecosystems, including coral reefs. Here we report a seven-week
experiment exploring the effects of ocean acidification on crustose coralline
algae, a cosmopolitan group of calcifying algae that is ecologically important
in most shallow-water habitats Six outdoor mesocosms were continuously
supplied with sea water from the adjacent reef and manipulated to simulate
conditions of either ambient or elevated seawater carbon dioxide concentrations.
The
recruitment rate and growth of crustose coralline algae (CCA) were
severely inhibited in the elevated carbon dioxide mesocosms. Our findings
suggest that ocean acidification due to human activities could
cause significant change to benthic community
structure in shallow-warm-water carbonate ecosystems.

...Although previous work examined the effects of calcium carbonate
saturation state on calcification rates of corals and coral communities
in realistic mesocosm studies, none has examined how community structure
may change under increasing degree of ocean acidification. ....
... Under high conditions, CCA recruitment rate and percentage cover
decreased by 78% and 92%, respectively, whereas non-calcifying algae increased
by 52% (Fig. 2) relative to controls. ....
... we did not attempt to replicate the natural compliment of herbivores
found on Hawaiian reef flats, and thus only microherbivores (for example
sea hares and amphipods) were in abundance. ...
... Under all proposed scenarios, continuous
anthropogenic emissions of CO2 to the atmosphere will result in a continuous
decline in the pH and calcium carbonate saturation state of ocean waters,
with all the ecological implications of such a change in a major Earth-surface-system
carbon reservoir. The only way to slow or prevent the continuing acidification
of surface ocean waters is to reduce the emissions of CO2 from human activities
to the atmosphere; however, because of the slow mixing rate of the oceans,
they will continue to be a major sink of anthropogenic CO2 emissions well
into the future, and ocean acidification will continue to intensify.
...
[sigh]

These scientists placed two times three plastic
cages (mesocosms) of 1x1x0.5m under water at shallow depth. The advantage
of this method is that the study mimics as closely as possible the natural
situation, including day-night light rhythm. In one set of three they manipulated
acidity to reflect a doubling of CO2 to 800ppm. Then they placed perspex
cylinders in each to see what would happen. In the control set they were
encrusted by crustose calcareous algae (CCA,'pink paint'), whereas in the
CO2-rich set they were encrusted by fleshy green algae. The differences
between the two sets were quite dramatic as shown by the photograph and
graphic. The conclusion is that man-made CO2 is bad, and that major
ecosystem changes can be expected. A final blow to the acid ocean skeptics.
End of debate. Period. ... Unless we examine the fine print and do
some detective work.

Crustose calcareous algae or pink paint
as divers call it, is a group of the most astounding organisms on our planet.
If you were told about stones that grew and replicated, you would disbelieve.
Yet it is true. CCA is living limestone, physically a red seaweed but without
any flesh or vessels. It grows in the shallows, exposed to ultraviolet
and low tide, yet forming extensive rocky platforms with caves and tunnels
in a mere 6000 years. On coral reefs it is the glue between stony corals,
forever scraped and nibbled at by urchins and fish, yet surviving and growing.
When algae peter out at the deep end of the photic zone, there is still
CCA and at twice that depth too. A boulder in a rock pool may be turned
by a storm, leaving its CCA cover buried in darkness. Yet turned back upright
after two months, the bleached CCA soon turns pink again, resuming business
as usual. When going from healthy waters to extremely degraded environments,
CCA is one of the last to give up. So come-on, why can this sturdy creature
not handle a little extra CO2? What is wrong we must ask? We
have some serious misgivings about this work for a variety of reasons.

Whenever a scientific article begins with 'anthropogenic
emissions' and 'IPCC', it raises the hairs on my back because
these people show to have a bias. Real science is about curiosity in about
how things work; not about 'proving' an idea. The experiment took only
seven (!) weeks (a student's summer holiday), immediately after which
the results were published - and accepted by the 'prestigious' journal
Nature!
The
experiment was not replicated; the cylinders were not swapped; mature
CCA was not investigated and so on. Instead these people focused on replicating
their publication: dial any of the authors (Kuffner or Jokiel will do)
on Google and see how many references and duplications come up. Other publications
were quick to refer to this shoddy work which is on a par with a school
science project.

For instance, it is equally interesting to see what
halving CO2 levels does, because the claim of 250ppm pre-industrial
level may be a myth. Why did the scientists not include a set of enclosures
for testing this? Note that this is a general criticism of most studies
of the effect of raised CO2.

The raised level of CO2 was not achieved by adding
CO2 to the water but a highly concentrated solution of hydrochloric
acid (HCl) that was trickled into the treatment enclosures. This releases
CO2 from the HCO3 species as discussed in the Bjerrum Plot above, but this
is not like the real world as it also diminishes the shell-building
CO3 ion. It also assumes various densities before diluting completely.
And even if this happens in the water above the cylinders, it will still
influence the plankton and spores and their settlement.

The experiment was not about death or slow growth
but about settlement. Algae have a two-phase life cycle: the mature
plant makes asexual spores that hatch into male and female plants, too
small to see, but these reproduce sexually, and their 'seeds' grow into
the colonies observed on the perspex cores, after first some time in the
plankton. Thus settlement is about the minute or hour that a 'seed' decides
to attach or not; a flash in a CCA's life. And that is all this experiment
was about.

Settlement is an extremely fickle (not constant,
uncertain) process. Put your plastic cores out, together with concrete
tiles, and you will see different creatures settle on each type. Put them
out today and it may be CCA that dominate. Next week could give barnacles.
Next month green algae and limpets, and so on. Settlement experiments
are almost impossible to replicate. Which means that they also have
little relevance. In the bar chart above, you can see some of that unpredictability.

Let me take you to the laboratory where these experiments
were done, at Kaneohe, Hawaii (photo below). The water here is not blue
as one would expect, but green. It is indicative of degradation
from eutrophication. Now look at the pH curves in the graph next to
it. The green curve shows the daily pH rhythm for the environment there.
For starters, average pH is well below 8.2, a sure sign of degradation.
The water here is already 50% more acidic than average ocean water. Now
look at how pH changes from mid day to mid night -0.3 units or 2x more
acidic, another sure sign of degradation. This is caused mainly by
decomposing planktonic bacteria, who never sleep. The bacterial activity
follows from the down slope of the curve in darkness, amounting to an RoA
(bacterial Rate of Attack) of 20-40 hion (see our DDA
method),
an indication that the environment here is under significant
stress. The point here is that all stresses add up, such that the extra
stress caused by high CO2, is only part of the whole and cannot be singled
out (see our principles of degradation
chapter).

Summarising it all: a naive study in a highly
stressed already acidic environment, using hydrochloric acid, not replicated
and perhaps not reproducible, with the low relevance of a settlement experiment.
Their far-reaching conclusions are not warranted by the experiment.

Abstract: Reef-building corals
are under increasing physiological stress from a changing climate and ocean
absorption of increasing atmospheric carbon dioxide. We investigated
328 colonies of massive Porites corals from 69 reefs of the Great
Barrier Reef (GBR) in Australia. Their skeletal records show that throughout
the GBR, calcification has declined by 14.2% since 1990, predominantly
because extension (linear growth) has declined by 13.3%. The data suggest
that such a severe and sudden decline in calcification is unprecedented
in at least the past 400 years. Calcification increases linearly with increasing
large-scale sea surface temperature but responds nonlinearly to annual
temperature anomalies. The causes of the decline
remain unknown; however, this study suggests that increasing temperature
stress and a declining saturation state of seawater aragonite may be diminishing
the ability of GBR corals to deposit calcium carbonate.
As we mentioned in previous articles, when a
scientific article begins with a reference to changing climate and
increasing
carbon dioxide, the authors show to have an agenda, a belief that is
bound to affect their studies. The bottom line reaffirms this belief with
increasing
temperature stress and declining saturation state of seawater aragonite.
Over 30% of this abstract is taken up by assertions that are not borne
out by the experiment, reason for extreme caution. We begin our critique
with this issue because it is exactly what the international press has
latched onto, inferring that this experiment proves corals declining BECAUSE
of anthropogenic carbon emissions, whereas nothing could be further from
the truth. Google for "de'ath coral" to see the massive damage done by
these statements that are irrelevant to the experiment.To take this criticism one step further, these
two statements secure the article a place in the 'prestigious' Science
journal which over the years has shown itself a firm global warming advocate,
together with other 'prestigious' journals such as Nature, Scientific
American, New Scientist and a host of others. The two statements
are also intended to secure continuation of funding. Reader beware!

What is Porites?The species of Porites corals grow slowly outward as a thin
peel around previous layers, thus slowly constructing 'massive' (meaning
solid) coral bommies. Their polyps are small and they appear smooth, a
'friendly' coral amongs the many sharp and sometimes stinging corals.

f044811: a diver in front of a large 'massive' Porites
coral in the clear waters of Niue island. The many christmas tree worms
are hardly visible on this scale.

f044135: christmas tree worms on Porites coral. These
beautiful fan worms are only a few centimetres tall, showing how small
the Porites coral polyps really are. Porites corals often include other
organisms like worms and molluscs in their matrix.

What was done?Previous studies have drilled cores into the 'massive' Porites
coral which can grow 'coral bommies' of several metres diameter and several
hundred years old. These cores from the Coral Core Archive were re-analysed
for their calcite (limestone) densities and growth rates, using state-of-the-art
scientific techniques of X-ray and gamma densitometry and simple length
measurements. Because corals live like plants, their growth rates depend
on temperature and the amount of light, both causing yearly bands, much
like tree rings. The cores investigated come from all over the north-south
extending Great Barrier Reef, allowing investigaters to also study the
effect of average temperature.

What
was found?The main finding of the study is shown in this graph for
extension
(blue, growth rate) (cm/yr) and density (green, g/ml), interpretation
of which is confusing. The increasing growth rate since 1900 suggests that
the sea has been warming, but it is accompanied by a reduction in density.
The product of the two is the calcification rate (red) with a flatter
mid-range. Its hockey-stick appearance of dipping down steeply since the
late-1990s has been cause for alarm, being clearly 'abnormal' as it has
not occurred in 400 years (not shown here). Normal growth of about 1.4cm
per year has suddenly dipped to less than 1.3cm/yr, a decline of 14.2%
per year, and should this trend continue, the porites coral could
disappear by the year 2050.

Conclusion:
The question is now what caused this sudden decline?

Do all Porites corals always end in an extension dip for the
past 6-8 years? After all, this is only 6x1.4= 8.4 cm into the coral
and it would be foolish to assume that the live polyps end at 1.4cm depth,
where they ended last year. In other words, at 8.4cm depth, calcification
may still be on-going, extending the coral colony outward as well, and
thus 'pulling' the hocky stick for extension up to 'normal' levels as time
proceeds. It is logical that where the polyp occupies space, calcification
is correspondingly less. Likewise one would not expect much woody tissue
in the shoots of a tree, which also extend over time. Ironically, this
suggestion has not been considered by the authors. In this context is is
important to know whether exceptions have been encountered, corals that
do not have a 'stunted growth' towards the present. See also the authors'
comment in next paragraph, suggesting that no exceptions were found. Darke&Barnes
[2] found that Porites polyps live on average for 2-3 years with a life
expectancy of 5 years. It suggests that some of the hockey stick 'nosedive'
is natural.

Is it caused by degradation from run-off from the land? This possible
cause is rejected out of hand by the authors even though coral reefs are
severely threatened by human proximity [1]: "Terrestrial runoff and
salinity, although potentially affecting inshore reefs, are also unlikely
causes because calcification declines at similar rates on offshore reefs
away from flood plumes". However, we (Anthoni) discovered that eutrophication
extends far beyond the reach of river plumes and visible runoff, reaching
the outer boundaries of continental shelves. Furthermore, when the water
is still deemed 'clear' (15m visibility), degradation has its worst effect
on sensitive organisms such as found in healthy reefs. To disprove degradation
as cause, coral cores must be extracted from areas remote from human settlement.
Note also that the authors are still unaware of our recent discoveries
about symbiotic decomposition and how corals derive growth in seas
devoid of food (nutrients and phytoplankton).

Is it caused by warming waters? The graph is contradictory as it
confirms that corals do better in warmer water, and also the authors find
no evidence along the temperature gradient from north to south along the
Great Barrier Reef. Sudden temperature events could do it but these have
to be frequent and would not produce a smooth decline as in the graphs.

Is it caused by ocean acidification? Unfortunately the coral cores
do not reveal ancient alkalinity (pH) and there exists no record of pH
measurements over the past 100 years. Besides, acidification is supposed
to have been a slow process, whereas the hockey stick suggests a sudden
disaster that began less than 10 years ago. Furthermore we have shown that
increased acidity benefits productivity in the oceans. No problem, let's
then introduce the notion of 'tipping point', a gradual GOOD process
suddenly becoming VERY BAD ??? Note that degradation can have a tipping
point which is different for each species. The difference between thriving
and dying is usually small (the tipping point); a company thrives when
it makes a profit but goes bankrupt from small losses.

Reader, as you can see, the study does not justify its conclusions:

"Laboratory experiments and models have predicted negative
impacts of rising atmospheric CO2 on the future of calcifying organisms.
Our data show that growth and calcification of massive Porites in the GBR
are already declining and are doing so at a rate unprecedented in coral
records reaching back 400 years. If Porites calcification is representative
of that in other reef-building corals, then maintenance of the calcium
carbonate structure that is the foundation of the GBR will be severely
compromised. Verification of the causes of this decline should be made
a high priority. Additionally, if temperature and carbonate saturation
are responsible for the observed changes, then similar changes are likely
to be detected in the growth records from other regions and from other
calcifying organisms. These organisms are central to the formation and
function of ecosystems and food webs, and precipitous changes in the biodiversity
and productivity of the world’s oceans may be imminent."

These scientists have discovered an interesting phenomenon but have not
been honest to the public. They did not disclose doubt and uncertainties,
and neither did they disclose any exceptions in the data (any exception
may prove the assumptions wrong). They knowingly and deliberately raised
the scare for ocean acidification and climate change, whereas
their experiment does not support this in any way.

Latest
update, August 2009. Busted for fraud!Steve McIntyre at Climate
Audit (June 2009) gives a chilling explanation of the Porites
slow-growth artefact: it is caused by a lack of data, as the dataset suddenly
drops from around 40-50 samples to only two! Besides, there is a mathematical
averaging problem that does not show in the long-term raw data.

The
raw data for average calcification shows a steady improvement in coral
growth with a sudden drop around the year 2000, not quite resembling the
graphs shown in the Science publication. But look at the pink histogram
on right, showing the number of datasets used for calculating this 'average'.
Since around 1984, this dataset has been declining to about 10, and in
2005 it dropped even further to 2! So all alarm is based on only two items!
Could one call this scientific fraud? Surely honest scientists would have
mentioned this in their publications?

Since this is one of the most quoted papers,
using the information of other scientists to invoke an enormous scare,
it is necessary for us to subject it to a critical dissection. This paper
is similar to that of the British Royal Society, dissected before. Note
that the authors believe that the predictions (scaremongering) of the IPCC
are correct, and that they base this paper entirely on this assumption.
The many experiments cited, done in laboratories and mesocosms all fail
to mimic the natural situation, as explained above in scientific
fraud. Some of the research quoted has even been debunked by us on
this page. In all, this paper sounds like a political manifesto.

AbstractOcean acidification is rapidly changing the carbonate
system of the world oceans. Past mass extinction events have been linked
to ocean acidification, and the current rate of change in seawater chemistry
is unprecedented. Evidence suggests that these changes will have
significant consequences for marine taxa, particularly those that
build skeletons, shells, and tests of biogenic calcium carbonate. Potential
changes in species distributions and abundances could propagate
through multiple trophic levels of marine food webs, though research into
the long-term ecosystem impacts of ocean acidification is in its infancy.
This review attempts to provide a general synthesis of known and/or hypothesized
biological and ecosystem responses to increasing ocean acidification. Marine
taxa covered in this review include tropical reef-building corals, cold-water
corals, crustose coralline algae, Halimeda, benthic mollusks, echinoderms,
coccolithophores, foraminifera, pteropods, seagrasses, jellyfishes, and
fishes. The risk of irreversible ecosystem
changes due to ocean acidification should enlighten the ongoing CO2 emissions
debate and make it clear that the human dependence on fossil fuels must
end quickly. Political will and significant large-scale investment
in clean-energy technologies are essential if we are to avoid the most
damaging effects
of human-induced climate change, including ocean acidification.

Reader, as you can see, most of the abstract is
scaremongering and is not supported by the uncertainties in the research
reviewed.

From the conclusion"The scientific knowledge base surrounding the biological effects of
ocean acidification is in its infancy and the long-term consequences of
changing seawater chemistry on marine ecosystems can only be theorized."
...."In contrast, the potential effects ocean acidification may have for
the vast majority of marine species are not known. Research into the synergistic
effects of ocean acidification and other human induced environmental changes
(e.g., increasing sea temperatures) on marine food webs and the potential
transformative effects these changes could have on marine ecosystems is
urgently needed." ..... "Future ocean acidification research needs include
increased resources and efforts devoted to lab, mesocosm, and in situ experiments,
all of which will aid in determining the biological responses of marine
taxa to increased pCO2. Mesocosm and in situ experiments may simulate and/or
provide more natural conditions than single-species lab experiments, but
they have thus far used abrupt changes in seawater chemistry which do not
allow for potential acclimation or adaptation by marine organisms."
[or
for the carbonate ion to develop].... "The shallow continental shelves
are some of the most biologically productive areas in the sea and are home
to the majority of the world’s fisheries, but accurate carbonate saturation
state data do not currently exist for most coastal regions." ..... "The
overwhelming volume of scientific evidence collated by the IPCC documenting
the dangers of human-induced climate change, of which ocean acidification
is only one, should end the lingering CO2 emissions reduction debate."...."The
global CO2 experiment which has been under way since the Industrial Revolution
and the potentially dire consequences this uncontrolled experiment poses
for marine organisms and indeed, all life on Earth, leave no doubt that
human dependence on fossil fuels must end as soon as possible. International
collaboration, political will, and large-scale investment in clean energy
technologies are essential to avoiding the most damaging effects of human-induced
climate change." [sigh . . are we detecting
a bias here?]

What is the study about?Taking a hand-picked IPCC projection as an unwavering fact, the authors
have hand-picked studies that show a decline in calcification for a wide
range of organisms, in higher concentrations of CO2 but not in lower concentrations.
To give an indication of their assumptions, study the table below which
has been taken in its entirety from the paper, in order to avoid making
any mistakes.

The table is based on our present knowledge of the ocean carbonate chemistry
[1,2], superimposed on the IPCC scare scenario. As
we have seen before, both are subject to considerable doubt and the ocean's
carbonate chemistry is also influenced by life. The columns represent milestones
in the time scale from glacial through preindustrial to the present and
beyond. The important rows are:

pCO2 in seawater: the IPCC myth of glacial CO2 concentrations of
180ppm, an equally mythical preindustrial concentration of 280ppm to the
present 380ppm (the only point with certainty), and from here on extrapolated
to twice and three times present concentration. If the first two assumptions
are wrong, the others just amplify the error.

temperature: from a glacial average global temperature of 15.7ºC
(perhaps) through a guessed at preindustrial temperature to the present
19.7ºC and beyond by extrapolation. Notice the disastrous 3ºC
global warming!

total pH: sinking from an extrapolated 8.32 through the present
8.05 to a future 7.76. These figures follow from pCO2 in seawater
(above) and are thus equally shaky.

carbonate ion: decreasing as if inside a laboratory test beaker
from an extrapolated 279 through the present 182 to an extrapolated future
of 115. The effect of the vast amount of buffering not taken into account
and Le Chatelier's principle flouted.

How did species react?The way species were subjected to increased levels of CO2 in the laboratory
(fraudulent science) gave alarming results:

None of the tested species reacted positively by increasing their calcification
rates. Other alarming results were noted for fishes, molluscs and cold
water corals. Only sea grasses and fleshy algae thrived. In all a very
alarming litany (listing) of bad news.

What are the uncertainties?Every scientific account should honestly mention doubts and uncertainties,
but this paper mentioned only "but they (scientists)
have thus far used abrupt changes in seawater chemistry which do not allow
for potential acclimation or adaptation by marine organisms". Yet the
whole paper is based on the very shaky predictions by the IPCC, mythical
values for the past and extrapolations based on these, a large uncertainty
about ocean chemistry, 'fraudulent' tests
and selective 'bad news' publications. In other words, the publication
was meant to be alarming from the beginning. We wonder when a more balanced
account may surface.

[1] Marsh, Gerald E : Seawater pH and anthropogenic
carbon dioxide. www.gemarsh.com.
"In 2005, the Royal Society published a report titled Ocean acidification
due to increasing atmospheric carbon dioxide. The report’s principal
conclusion—that average ocean pH could decrease by 0.5 units by 2100—is
demonstrated here to be consistent with a linear extrapolation of very
limited data. It is also shown that current understanding of ocean
mixing, and of the relationship between pH and atmospheric carbon dioxide
concentration, cannot justify such an extrapolation."[2] There are two conflicting 'knowledges' of ocean chemistry:
Pearson&Palmer hold the total of all CO2 species constant whereas Caldeira&Berner
hold the CO3 ion constant, resulting in radically different relationships
between CO2 concentration and pH. To make matters worse, Le Chatelier principle
holds that all CO2 species change, and on top of it all, life has its own
influence (growth and decay)And concentrations inside the organism are
different from those outside.

Further studiesAs further scientific studies appear, the case for a fear of ocean
acidification becomes snmaller and smaller. In this chapter we'll summarise
those studies debunking ocean acidification as their numbers increase.
As we will continue to focus on fraudulent aspects of scientific studies,
others have kept an eye on dozens to thousands of studies so far.

The three researchers report that just the opposite of
what is often predicted actually happened, as the echinoderm larvae and
juveniles were "positively impacted by ocean acidification." More specifically,
they found that "larvae and juveniles raised at low pH grow and develop
faster, with no negative effect on survival or skeletogenesis within the
time frame of the experiment (38 days)." In fact, they state that the sea
stars' growth rates were "two times higher" in the acidified seawater;
and they remark that "C. papposus seem to be not only more than
simply resistant to ocean acidification, but are also performing better."

go to part 1, introduction and
conclusion <==> go to part3, uncertainties
and missing knowledge.